Method and apparatus for treating shale gas waste water

ABSTRACT

Organo clay and activated carbon are mixed to form a particle mixture. The particle mixture is contacted with waste water having chlorides and other contaminants, such as organic materials, heavy metals, chlorides, and low level radio nuclei in solution. Acids, oxidizing chemicals, and compressed air are added to pretreat and to treat the waste water. The mixture is filtered with catalytic activated carbon filters to remove the remaining contaminants. The filters produce a clean chloride solution that is discharged or is subjected to a finishing process to produce a marketable chloride product.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 14/120,455filed May 20, 2014 which is a division of U.S. application Ser. No.12/924,315 filed Sep. 24, 2010, now U.S. Pat. No. 8,727,007, whichclaims the benefit of U.S. Provisional Application No. 61/277,493 filedSep. 25, 2009.

BACKGROUND OF THE INVENTION 1. Field of the Invention

This invention relates to a method and apparatus for treating shale gaswaste water that includes dissolved chlorides and, more particularly, toa method and apparatus for producing a chloride-based product from aclean chloride solution obtained through a waste water treatmentprocess.

2. Description of the Related Art

Purified water is used in many industries including the chemical,foodstuffs, electronics, power, medical and pharmaceutical industries,as well as for human consumption. Typically, prior to use in any one ofthese fields, the water is treated to reduce the level of contaminantsto acceptable levels. These treatment techniques include disinfection,distillation, filtration, ion exchange, reverse osmosis, photooxidation,ozonation, and combinations thereof.

Various levels of purity may be required for different end uses. Waterquality may be regulated by various government agencies and tradeorganizations including the U.S. Environmental Protection Agency (EPA)and the Food and Drug Administration (FDA).

One field in which the treatment of water is necessary is in the naturalgas extraction field. Extracting natural gas trapped in shale formationsand other gas reservoirs often requires the use of hydraulic fracturing(also known as “fracing” or “well stimulation”). Fracing has been usedsafely and effectively for over sixty years. The goal of the fracingprocess is to create a pathway of man-made cracks in the rock that allowgas to flow from the shale into the wellbore. Without this technique,many natural gas reservoirs would not produce natural gas.

The fracing process is very water intensive, so that steps must be takento protect groundwater. In very tight rock formations (i.e. rockformations in which gas cannot migrate through the formation naturally),a greater amount of water is used to stimulate the fractures and enhancegas flow. These formations require more water than a traditional shallowwell.

The fracing of a shale well takes place after the well has reached adesired vertical and/or horizontal depth and can last for several days.Once well casing is cemented in place to protect the water aquifers andgas production zones, a charge is fired into the formation at the end ofthe wellbore. It perforates the steel casing, cement and shale formationto provide a pathway for the fresh water injection.

Fluids pumped under pressure act as a wedge to crack the rock duringfracing operations. The fluid includes water, sand, and special-purposeadditives that are injected into the wellbore. The additives are mixedin self-contained systems where fluids are not exposed to theenvironment. Some of the additives are commonly referred to as“slickers” or “slicker” chemicals.

Some additives include acids, such as hydrochloric acid or muriaticacid, which dissolve minerals and initiate cracks in the rocks, andanti-bacterial agents, such as glutaraldehyde, which eliminate bacteriain the water that produce corrosive by-products. Breakers, such asammonium persulfate, that allow for a delayed break down of the gel arealso used to thicken the water in order to suspend the sand. Corrosioninhibitors, such as n,n-dimethylformamide, are also used to prevent thecorrosion of pipe.

Common additives also include crosslinking agents, such as borate salts,that maintain fluid viscosity as temperature increases, and gels, suchas Guar gum or hydroxyethyl cellulose, that thicken the water in orderto suspend the sand. Other common additives include chemicals forcontrolling iron content, such as citric acid, which prevent theprecipitation of metal oxides, and potassium chloride that creates abrine carrier fluid.

Oxygen scavengers, such as ammonium bisulfate, are used to remove oxygenfrom the water to protect pipes from corrosion. Other common additivesinclude pH adjusting agents, such as sodium or potassium carbonate, formaintaining the effectiveness of other components such as thecrosslinking agents.

Other additives also include proppants, such as silica or quartz sand,which allows the fractures to remain open so that the gas can escape,and scale inhibitors, such as ethylene glycol, which prevent scaledeposits in the pipe. Surfactants, such as isopropanol, are also used toincrease the viscosity of the fracture fluid.

A significant portion of the fluid returns to the surface through theprotective casing. It is highly monitored, collected and saved in tanksor lined pits on the well site for later transport to permitted disposalfacilities. This returned fluid, called “flowback,” can pick up heavysalts and minerals.

Additional amounts of water used in the fracing process remain in theshale formation nearly a mile below the Earth. The remaining waterreturns slowly over time at the well site and is redirected intocollection tanks where it is removed and treated.

The fracing process produces a waste water stream that is contaminatedwith multiple contaminants, namely oil/grease, soluble organics, heavysalts, minerals, trace metals, extremely high concentration ofchlorides, and, optionally, radioactive nuclei. Since the need toprotect ground water is great, the waste water must be treated to removethe contaminants so that the waste water does not contaminate the groundwater.

Many methods for treating waste water are known. U.S. Patent PublicationNos. 2008/0116136 and 2009/0045135 disclose general methods for treatingwaste water. Other methods include methods for removing metals,particularly heavy metals, such as the method disclosed in U.S. Pat.Nos. 3,761,381, 4,157,942, 4,171,255, and 4,652,352.

U.S. Pat. No. 4,652,352 discloses a method for recovering heavy metalsfrom dilute solutions. U.S. Pat. Nos. 3,761,381, 4,157,942 and 4,171,255disclose methods for recovering heavy metals from aqueous solutions.

U.S. Pat. No. 6,214,233 discloses a method for treating a waste waterstream that contains cyanide bearing compounds and heavy metals, such ascopper, silver, nickel, and iron. The method utilizes a strippingsolution to remove adsorbed metals from adsorption materials.

U.S. Pat. No. 5,770,090 discloses a method for treating a waste waterstream that contains heavy metals, such as chromium, zinc, and copper.The method utilizes activated carbon as an adsorption material. Themethod also utilizes a stripping solution to remove the adsorbed metalsfrom the adsorption material.

U.S. Pat. No. 3,973,987 discloses a water recycle treatment system. Thesystem feeds treated water to a distillation unit to precipitate themetals and salts in sludge and also forms a water vapor output.

Other methods for treating waste water are directed to methods andapparatus for removing organic compounds from the water. U.S. Pat. No.4,929,359 discloses a method for treating highly concentrated and toxicpetroleum-based and synthetic fuels waste waters, such as oil shaleretort water using electrolysis. The treatment is performed in a reactorthat contains polyurethane foams.

U.S. Pat. No. 7,441,665 discloses a water purification cartridge. Thewater purification cartridge includes porous diatomaceous earthenceramic water filters or carbon filters packed with granulated activatedcarbon or block.

U.S. Pat. No. 6,709,585 discloses a waste water purification system. Thesystem includes a tank-filter for performing a pre-treatment step. Thetank includes a flocculant that is uniformly mixed with an agitator. Thepretreated water is directed to a collecting tank for clarification. Theclarified, pre-treated water is directed through a safety filter to abattery of activated carbon columns for treatment. In anotherembodiment, a polypropylene bag filter that includes diatomaceous earthis used to pre-treat the waste water.

Many waste water treatment methods utilize diatomaceous earth oractivated carbon. U.S. Pat. No. 4,568,463 discloses a method andapparatus for purifying aqueous solutions. A diatomaceous earth coarsefilter is used to pre-treat the solution. An activated charcoal columnis used to finish the process. Optionally, chloride is utilized to killmicroorganisms.

U.S. Pat. No. 4,454,044 discloses a water treatment process. The processinvolves contacting water with a relatively small amount of diatomaceousearth particles or activated carbon particles to adsorb impurities.After contact with the particles, the water is passed through a filter.

U.S. Pat. No. RE 35,871 discloses a water reclamation system for carwashes. The system uses a diatomaceous earth filter for removingparticulates and a carbon filter for removing organic contaminants. Thediatomaceous earth filter removes particles of dirt, oil, and rust. Thecarbon filter includes activated charcoal that removes dissolved organicmaterials, such as oil and surfactants. The system also utilizeschloride or ozone to kill algae.

Other methods for treating water are directed to desalination methods. Apublication entitled “Capacitive Deionization Technology™: Analternative desalination solution” by T. J. Welgemoed and C. F. Schutte,Desalination 183 (2005) at 327-40, discloses that possible desalinationtechniques for brackish water include reverse osmosis, electrodialysis,and a low-pressure non-membrane desalination process that is identifiedby the trademark Capacitive Deionization Technology™.

A publication entitled “Desalination technology could clean upwastewater from coal-bed methane production” by K. Christen,Environmental Science & Technology Online News, Jan. 11, 2006, accessedhttp://pubs.acs.org on Oct. 28, 2008, discloses that such technologiescan be used in the treatment of waste water from coal-bed methaneproduction.

However, none of the above described water treatment methods areeffective in treating the waste water streams that include thecombination of oil and grease, soluble organics, trace metals, andextremely high concentration of chlorides that are produced in “fracing”operations in the extraction of natural gas from shale formations.Accordingly, an improved waste water treatment is needed.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided a method fortreating water. A stream of brine water having in solution organicmaterials, heavy metals, and chlorides with at least a portion of theorganic materials forming an emulsion within the brine water isprovided. Organo clay is mixed with particles of activated carbon toform a particle mixture for treating the stream of brine water. Theparticle mixture is contacted with the stream of brine water to removethe organic materials and the heavy metals from the stream of brinewater. The particle mixture and stream of brine water is filtered toremove the particles of activated carbon to form a clean chloridesolution.

Further in accordance with the present invention, there is provided amethod for treating an aqueous chloride solution. An aqueous chloridesolution having heavy metals and organic compounds with at least aportion of the organic compounds forming an emulsion and a portion ofthe organic compounds including toxic organic compounds therein isprovided. The aqueous chloride solution is pretreated to remove at leasta portion of the organic compounds and heavy metals. The pH of theaqueous chloride solution is lowered to break down the emulsion. Theaqueous chloride solution is oxidized to remove the toxic organiccompounds. The aqueous chloride solution is passed through a filter toform a clean chloride solution.

Further in accordance with the present invention, there is provided amethod for treating water. A stream of brine water having in solutionorganic materials, heavy metals, and chlorides with a portion of theorganic materials forming an emulsion therein is provided. Organo clayis mixed with particles of activated carbon, an acid selected from thegroup consisting of organic acids and mineral acids, and a peroxidecompound to form a particle mixture for treating the stream of brinewater. The particle mixture is contacted with the stream of brine waterto remove the organic materials and the heavy metals from the stream ofbrine water. The particle mixture and the stream of brine water isdirected into a filter system having a catalyst to form a clean chloridesolution.

Accordingly, a principal object of the present invention is to provide amethod for treating waste water.

Another object of the present invention is to provide a method forremoving organic compounds, oil and grease emulsions, and heavy metalsfrom an aqueous chloride solution.

Another object of the present invention is to provide a method suitablefor producing a chloride-based product from a clean chloride solution.

A further object of the present invention is to provide a method fortreating a waste water by-product from shale oil and gas production.

A further object of the present invention is to provide a methodsuitable for treating shale gas brine waste water via catalyticactivated carbon.

These and other objects of the present invention will be more completelydescribed and disclosed in the following specification, accompanyingdrawings, and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a conceptual flow diagram illustrating a two-part method fortreating waste water having a pretreatment step and a catalytic carbonfiltering step.

FIG. 2 is a conceptual flow diagram of the method shown in FIG. 1,illustrating an electrochemical chloride production step.

FIG. 3 is a process flow diagram for the method shown in FIG. 2.

FIG. 4 is a conceptual flow diagram of the method shown in FIG. 1,illustrating a chemical chloride production step.

FIG. 5 is a process flow diagram for the method shown in FIG. 4.

FIG. 6 is a conceptual flow diagram of the method shown in FIG. 1,illustrating a distillation step.

FIG. 7 is a process flow diagram for the method shown in FIG. 6.

FIG. 8 is a conceptual flow diagram of the method shown in FIG. 1,illustrating effluent injected into a deep well.

FIG. 9 is a process flow diagram for the method shown in FIG. 8.

FIG. 10 is a conceptual flow diagram of the method shown in FIG. 1,illustrating a reverse osmosis step.

FIG. 11 is a process flow diagram for the method shown in FIG. 10.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring to the drawings and particularly to FIG. 1, there isillustrated apparatus, generally designated by the numeral 10, forperforming a method for treating waste water, particularly waste waterthat has been obtained from fracing operations within a shale formation.The apparatus 10 is suitable for treating waste water streams thatinclude brine water having organic materials, heavy metals, andchlorides in solution. Some of the organic materials form oil and greaseemulsions within the waste water. The waste water also includes traceamounts of normally occurring radio nuclei or NORMS, such as low-levelradio nuclei.

The chlorides are present in the waste water stream as a result of theadsorption of chloride from the shale formation into solution. Theadsorption of chloride results in the formation of dissolved chloridesin the solution. The chloride concentration typically ranges from 20,000ppm to 250,000 depending upon the number of times the waste water hasbeen cycled through the shale formation.

As shown in FIG. 1, the apparatus 10 is particularly adapted to treat atleast two different types of waste water streams. The first type ofwaste water stream has been cycled through a shale formation at leastone time. The chloride concentration of the waste water from these typesof waste water streams will include up to about 80,000 ppm from thiscycle.

The second type of waste water stream has been cycled through a shaleformation as many as five times or more. The chloride concentration ofthe waste water from these types of streams will be as much as about250,000 ppm. Typically, the chloride concentration ranges from 50,000ppm to 225,000 ppm.

The waste water for both types of waste water streams also includesheavy metals, such as iron, aluminum, magnesium, and zinc, and solubleorganics, such as benzene, xylene, toluene, and phenols. The waste watertypically includes an emulsion that is formed from oil and grease. Thewaste water also includes trace amounts of radioactive nuclei, barium,or a combination of both.

Sequence No. 1

Referring to FIG. 1, the apparatus 10 includes a pretreatment unit 12, aclarification unit 14, a filtration unit 16, and a carbon cleaningsystem 18. The apparatus 10 removes the organic materials and the heavymetals from the waste water. The apparatus 10 also breaks down the oiland grease emulsion within the waste water to produce an essentiallyclean chloride solution.

The pretreatment unit 12 treats the waste water to produce a pretreatedchloride solution. The pretreatment unit 12 is connected in series withthe clarification unit 14, which produces a clarified pretreatedchloride solution. The clarification unit 14 is connected in series tothe filtration unit 16, which removes the remaining contaminants in theclarified pretreated chloride solution to produce the clean chloridesolution.

As shown in FIG. 1, the carbon cleaning system 18 connects to thefiltration unit 16 to reactivate filter media within the filtration unit16. The carbon cleaning system 18 utilizes clean water to produce astripping solution that regenerates the filter media. The regeneratedfilter media is recycled back into the filtration unit 16. The strippingsolution is directed to pretreatment unit 12 for recirculation throughthe apparatus 10.

The pretreatment unit 12 receives raw waste water (brine water) fortreatment with a combination of activated carbon, organo clay materials,acids, and oxidizing chemicals. Optionally, the mixture is combined withcompressed air to enhance the pretreatment step. The pretreatment unit12 produces a pretreated chloride solution for the clarification unit14.

The organo clay materials adsorb heavier organic compounds within thewaste water stream. The activated carbon in either powdered or granularform adsorbs other soluble organic compounds and the heavy metals in thewaste water stream. The acids lower the pH of the waste water stream tobreak down emulsions. The oxidizing chemicals remove toxic organiccompounds.

As shown in FIG. 1, the pretreated chloride solution is conveyed fromthe pretreatment unit 12 to the clarification unit 14 throughconventional methods. The clarification unit 14 separates certain solidparticles from the mixture pretreated chloride solution for disposal ina landfill. In addition, a selected portion of the solid particles fromthe clarification unit 14 are recycled back to the pretreatment unit 12into contact with the stream of brine water. The clarification unitproduces a clarified pretreated chloride solution for the filtrationunit 16.

The clarified pretreated chloride solution is conveyed throughconventional methods to the filtration unit 16 to perform a catalyzedfiltration step. The filtration unit 16 includes a pair of filters 20,22 that are impregnated with catalyst materials to enhance the removalof contaminants from clarified pretreated chloride solution.

The filtration unit 16 receives acids that break down remainingemulsions and oxidizing chemicals that remove residual toxic organiccompounds. Optionally, compressed air enhances the effectiveness of theacids, oxidizing chemicals, and the filters 20, 22 within the filtrationunit 16.

As shown in FIG. 1, the filters 20, 22 remove the remaining organiccompounds, heavy metals, and radio nuclei within the clarifiedpretreated chloride solution. Preferably, the filters 20, 22 have theability to remove trace amounts of the organic compounds, heavy metals,and radio nuclei.

The spent carbon from the filters 20, 22 is directed by conventionalmethods to a carbon cleaning system 18 for treatment. Clean water isadded to the carbon cleaning system 18 to form a stripping solution toclean the spent carbon. The stripping solution is pumped to thepretreatment unit 12 for re-circulation within the apparatus 10.

Once the stripping solution cleans the spent carbon, the carbon isreactivated through a reactivation step in a reactivation system 24through any suitable reactivation method. Preferably, the spent carbonis thermally reactivated and directed back to the filters 20, 22 forre-use.

As shown in FIG. 1, the filtration unit 16 produces a clean chloridesolution that is suitable for disposal or for subsequent processing toobtain chloride-based chemical products. The clean chloride solution issubject to one or more finishing processes, such as chemical productproduction, electrochemical production, or distillation to produce achloride chemical product. Alternatively, the clean chloride solution issuitable for reverse osmosis or deep well injection.

Sequence No. 2

Referring now to FIGS. 2-3, another embodiment of an apparatus,generally designated by the numeral 26, for treating a brine waste waterstream from a shale formation in which like elements are identified bylike numerals shown in FIG. 1. The apparatus 26 includes a pretreatmentunit 12, a clarification unit 14, a filtration unit 16, a carboncleaning system 18, and a finishing unit 28.

The pretreatment unit 12 includes a mixing tank 30 for receivingactivated carbon particles 32 and organo clay 34 to form a particlemixture.

As shown in FIGS. 2-3, the pretreatment unit 12 blends particles ofactivated carbon with an organo clay material in the mixing tank 30 toproduce a mixture for treating the waste water stream. The organo claymaterial adsorbs the heavier organic compounds. The activated carbonadsorbs other soluble organic compounds and the heavy metals in thewaste water stream.

The pretreatment unit 12 mixes the activated carbon particles with theorgano clay material to form a particle mixture for treating the wastewater stream. The activated carbon particles and the organo clay aremixed in step 12 in any suitable proportion to treat the waste waterstream. Preferably, the activated carbon particles are coated with theorgano clay before being added to the waste water stream.

The activated carbon particles 32 and the organo clay 34 are mixed inany suitable proportion to treat the waste water stream. Suitableproportions include ratios of activated carbon to diatomaceous earthranging from 100:1 to 1:1. Preferably, the activated carbon particles 32and organo clay are mixed in ratios of activated carbon to organo clayfrom about 50:1 to 15:1.

Suitable activated carbon particles include particles made fromactivated charcoal, activated coal, or any form of porous carbon havinga large degree of surface area that is available for adsorption orchemical reaction. Suitable activated carbon particles are prepared frompowdered activated carbon, granulated activated carbon, extrudedactivated carbon, impregnated activated carbon, polymers coated carbon,or any other suitable source of activated carbon. Preferably, theactivated carbon particles 32 include granulated activated carbonparticles.

Referring to FIGS. 2-3, the organo clay 34 includes any suitableorgano-clay or clay-organic complex that includes phyllosilicates,smectites, vermiculites, kaolins, diatomaceous earth compounds, or othersimilar compounds. Preferably, the organo clay 34 includes diatomaceousearth compounds, such as certain well-known mineral compounds havinghigh adsorption and low bulk density.

Suitable diatomaceous earth compounds also include naturally occurringsaltwater diatomaceous earth, naturally occurring freshwaterdiatomaceous earth, calcined diatomaceous earth, celite, perlite, andman-made compounds that include essentially identical or equivalentcompositions to naturally occurring diatomaceous earth compounds.

The use of diatomaceous earth adds sodium to the waste water, whichimproves brine recovery. Certain raw waste water compositions do nothave a sufficient ratio of sodium to chloride to complete the recoveryof the chloride as a high purity salt material. The use of diatomaceousearth increases the sodium concentration of the waste water byapproximately 60%.

As shown in FIG. 3, the mixture of activated carbon particles and organoclay is conveyed by pumping to a second mixing tank 36. Within themixing tank 36, the particle mixture contacts the brine waste waterstream 38 to remove contaminants.

Chemicals are injected into the waste stream 38 to enhance the abilityof the particle mixture to remove contaminants. The chemicals includeacids for lowering the pH to break down the oil and grease emulsionwithin the waste water stream. The chemicals also include oxidizingchemicals that add oxygen to the solution to act as a catalyst to reducethe toxicity of certain soluble organic materials within the solution.

The particle mixture of activated carbon and organo clay is mixed withthe waste water stream in the mixing tank 36 for a predetermined amountof time to remove the organic materials and the heavy metals.Preferably, the particle mixture produced contacts the waste waterstream for a period of time between fifteen minutes to two hours.

The pretreatment unit 12 injects compressed air 40 to facilitate theremoval of the organic materials and the heavy metals from the wastewater stream 38. Preferably, the pretreatment unit 12 utilizes lowpressure compressed air. Optionally, the waste water stream 38 issubject to agitation (not shown) to further enhance the removal of thecontaminants and produce a pretreated chloride solution.

As shown in FIG. 3, at least one oxidizing chemical 42 and acids 44 areadded to the particle mixture and the waste water to enhance the removalof contaminants.

The oxidizing chemical 42 includes any suitable chemical or combinationof chemicals that add oxygen to the solution, such as peroxides,chlorates, perchlorates, nitrates, and permanganates. The oxidizingchemical 42 also acts as a catalyst to reduce the toxicity of solubleorganic materials within the solution. Preferably, the oxidizingchemical 42 includes a peroxide compound, such as a hydrogen peroxide.

The acids 44 include any suitable acid that lowers the pH of the wastewater solution. Suitable acids include mineral acids, such ashydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boricacid, hydrofluoric acid, and hydrobromic acid, or organic acids, such aslactic acid, acetic acid, formic acid, citric acid, or oxalic acid.Preferably, the acids 44 include only organic acids.

Further, as shown in FIG. 3, the particle mixture, the compressed air40, the oxidizing chemical 42, and the acids are mixed together andcontact the waste water stream 38 simultaneously in the mixing tank 36.Optionally, the particle mixture, the compressed air 40, the oxidizingchemical 42, and the acids 44 are added in series. Alternatively, one ormore of the compressed air 40, the oxidizing chemical 42, and the acids44 are omitted.

The mixing tank 36 is a conventional mixing tank having predetermineddimensions and is constructed from any suitable materials. The mixingtank 36 includes a suitable filter for separating solid waste from thetreated waste water stream. Preferably, the filter is a 20 microncartridge filter.

Once the waste water stream 38 is pretreated in the mixing tank 36, thewaste water stream 38 is conveyed to a clarification unit 14 to separatethe particles within the particle mixture and other solid waste from thepretreated chloride solution. The clarification unit 14 is a gravityseparation device or any other suitable separation device. Preferably,the clarification unit 14 is a lamella clarifier.

The clarification unit 14 produces a clarified pretreated chloridesolution that is directed to the filtration unit 16. Preferably, thefiltration unit 16 is a two stage filtration system that includes a pairof filters 20, 22 connected in series. The filters 20, 22 produce aclean chloride solution suitable for discharge or for subsequentprocessing.

The filters 20, 22 include activated carbon filters impregnated with oneor more catalysts therein. Preferably, the filters 20, 22 includecatalytic activated carbon filters formed from beds of activated carbon.The activated carbon beds are positioned within tanks and are pretreatedto have a predetermined pH level to enhance the adsorption of theresidual heavy metals, organic compounds, and low level radionuclei inthe clarified pretreated chloride solution. Optionally, the filtrationunit 16 includes a controller (not shown) for controlling the pH levelof filters 20, 22 to optimize the removal of the contaminants from thewaste water stream 38.

The filters 20, 22 shown in FIG. 3 are configured in a predeterminedarrangement and are constructed from any suitable materials using anysuitable fabrication process. A suitable arrangement includes twoidentical adsorber tanks arranged in the manner set forth in U.S. Pat.No. 6,214,233, which is incorporated herein by reference, which areidentical in design and commercially available from Tigg Corporation.Both tanks utilize granular activated carbon from Calgon Carbon Corp.under the trademark “Filtrasorb 400” and are fabricated of steel andskid mounted. Each tank includes conventional pipes, valves, andfittings. The tanks are lined with an abrasion flake glass coatingavailable from Ceilicote Coatings, Inc.

Upstream of the first filter 20, compressed air 46, an oxidizingchemical 48, and an acid 50 are added to the pre-treated waste water toremove additional contaminants. After the solution has been filtered fora predetermined residence time, the solution is directed to the secondfilter 22 for additional filtering.

Unlike the filter media within the adsorber tanks in in U.S. Pat. No.6,214,233, the filters 20, 22 include catalyst material that is embeddedor impregnated therein. The selection of the catalyst material is notcritical. Preferably, the catalyst material is a metal impregnatedcatalyst material that includes a suitable metal impregnated on theactivated carbon, such as titanium, vanadium, chromium, cobalt, nickel,copper, iron, molybdenum, manganese, gold, silver, palladium, platinum,or a combination thereof.

As shown in FIG. 3, the spent carbon from the filters 20, 22 is directedby pumping to a regeneration mixing tank 52 within the carbon cleaningsystem 18 for treatment. Clean water 54 is added to the mixing tank 52to form a stripping solution 56 to clean the spent carbon. The strippingsolution 56 is pumped to the mixing tank 36 for re-circulation withinthe apparatus 26.

The carbon cleaning system 18 operates in a manner similar to the systemfor regenerating the adsorber tanks that is disclosed in U.S. Pat. No.6,214,233, in which the tanks are separately regenerated. The carboncleaning system 18 includes valves, pumps, and, optionally, probessimilarly arranged in a predetermined configuration,

As further shown in FIG. 3, a conventional pumping mechanism (notshown), such as a pump or a plurality of pumps, first directs the cleanwater 54 through an open and closed sequence of valves in a closed loopthrough the regeneration mixing tank 52 to form the stripping solution56. The stripping solution 56 is directed upwardly to the mixing tank 36and back to the regeneration mixing tank 52. After regeneration bothfilters 20, 22 are opened to allow the stripping solution remaining toflow back to regeneration mixing tank 52.

Once the stripping solution 56 cleans the spent carbon, the carbon isreactivated through a reactivation step in a reactivation system 58through any suitable reactivation method. Preferably, the spent carbonis thermally reactivated and directed back to the filters 20, 22 forreuse.

The filtration unit 16 produces a clean chloride solution from thefilter 22. Initially, the filtration unit 16 removes a substantialfraction of the chloride from the solution, as much as 75% or morechloride from a solution that initially includes 80,000 ppm ofchlorides. After a predetermined amount of time, the filtration unit 16will remove from between 10% to 12.5% of the chlorides from the cleanchloride solution.

As shown in FIG. 3, the clean chloride solution is directed to a mixingtank 60 within the finishing unit 28 for producing metal halideproducts, particularly metal-chloride compounds. The finishing unit 28includes a direct current power source 62, a cathode 64, and asacrificial anode 66 for electrochemical chloride production. Thecathode 64 and the anode 66 are positioned within the mixing tank 60.The clean chloride solution contacts at least a portion of the cathode64 and the sacrificial anode 66.

As shown in FIG. 3. The cathode 64 and the anode 66 are electricallyconnected to the power source 62 so that the power source 62, thecathode 64, the anode 66, and the clean chloride solution form anelectrochemical cell for producing a chloride product.

The anode 66 is formed from any suitable metal product that has theability to react with the chloride within the chloride solution to forma chloride product. Suitable metal products include zinc, copper, iron,nickel, cobalt, manganese, or other metals that form chloride compounds.The chloride products precipitate from the solution to form the chloridecompounds, such as zinc chloride, cupric chloride, ferric chloride,nickel chloride, cobalt chloride, and manganese chloride.

A portion of the chloride solution is directed to a collection tank 68for collection of the chloride products. The collection tank 68 includesa filter 70 to facilitate collection of the products. The collectedproducts are stored in a storage tank 72. The remainder of the chloridesolution is directed to a filter 74 for additional filtration anddischarge.

Sequence No. 3

Referring now to FIGS. 4-5, there is illustrated another embodiment ofan apparatus for treating waste water generally designated by thenumeral 76 in which like elements are identified by like numerals shownin FIGS. 1-3. The apparatus 86 includes a pretreatment unit 12 havingthe first mixing tank 30 for coating activated carbon particles withorgano clay and the second mixing tank 36 for pretreating the brinewaste water stream 38. The apparatus 76 also includes the clarificationunit 14, the filtration unit 16, and the carbon cleaning system 18 forrecycling spent carbon from the filtration unit 16.

Unlike the embodiments shown in FIGS. 1-3, the apparatus 76 includes afinishing unit 78 for the production of chloride compounds from theclean chloride solution. The finishing unit 78 includes a mixing tank80, shown in FIG. 5, for receiving the clean chloride solution and achloride reagent storage unit 82 that directs chemical reagents into themixing tank 80 to produce chemical products.

The mixing tank 80 directs the portion of the solution to a collectingtank 84 that includes a filter 86 for recovering the chemical productfrom the solution. The filter 86 is connected in series with a storagetank 88 for storing the chemical product. The remaining portion of thesolution is directed to a filter 90 for polishing and discharge aseffluent from the apparatus 76.

As also shown in FIG. 5, the reagent storage unit 82 stores a suitablereagent for reacting with the chloride in the clean chloride solution inmixing tank 80 to form a suitable chloride compound. Suitable reagentsinclude carbonate-based materials, such as zinc carbonate, oxide basedmaterials, such as zinc oxide, or hydroxide materials, such as calciumhydroxide.

Sequence No. 4

Referring now to FIGS. 6-7, there is illustrated another embodiment ofan apparatus for treating waste water generally designated by thenumeral 92 in which like elements are identified by like numerals shownin FIGS. 1-5. The apparatus 92 includes a pretreatment unit 12, aclarification unit 14, a filtration unit 16, and a carbon cleaningsystem 18.

Unlike the embodiments shown in FIGS. 1-5, the apparatus 92 includes afinishing unit 94 shown in FIG. 7, that includes a distillation unit 96that receives the clean carbon solution from the filtration unit 16.Preferably, the distillation unit 96 includes a chemical that maintainsthe pH of the clean chloride solution within the distillation unit 96 ata predetermined level.

The distillation unit 96 is connected to a suitable thermal energysource that provides thermal energy to facilitate distillation of waterfrom one fraction of the clean chloride solution, which is directed to acollection tank 98 and a storage tank 102. The other fraction isdirected to a filter 104 prior to discharge.

The collection tank 98 collects the salt residue from the clean chloridesolution. The storage tank 102 holds the residual salt product, which issuitable for use in commercial applications.

Sequence No. 5

Referring now to FIGS. 8-9, there is shown another embodiment of anapparatus for treating waste water generally designated by the numeral106 in which like elements are identified by like numerals shown inFIGS. 1-7. The apparatus 106 includes the pretreatment unit 12, theclarification unit 14, the filtration unit 16, and the carbon cleaningsystem 18.

Unlike the embodiments shown in FIGS. 1-7, the apparatus 106 isparticularly adapted for deep well injection 108 of the clean chloridesolution. Injection of the raw waste stream, which includes organiccompounds, heavy metals, oil and grease, barium, and radio nuclei, intoa deep well is undesirable.

Mixing the contaminants in the raw waste water with the ground water canplug up drilling equipment and contaminate the ground water. The watertreatment provided by the apparatus 106 removes a sufficient quantity oforganic compounds, heavy metals, and oil and grease to make deep wellinjection environmentally feasible.

The location of the deep well relative to the apparatus 106 is notcritical. Preferably, the clean chloride solution is produced by theapparatus 106 at one site and transported to the deep well.Alternatively, the apparatus 106 is located at a site that is adjacentto the deep well.

Sequence No. 6

Referring now to FIGS. 10-11, there is shown another embodiment of anapparatus for treating waste water generally designated by the numeral110 in which like elements are identified by like numerals shown inFIGS. 1-9. The apparatus 110 includes the pretreatment unit 12, theclarification unit 14, the filtration unit 16, and the carbon cleaningsystem 18.

Unlike the embodiments shown in FIGS. 1-9, the apparatus 110 isparticularly adapted for performing a reverse osmosis step 112 on theclean chloride solution. The apparatus 110 includes a filter 114 that isspecially adapted for reverse osmosis operations.

A typical reverse osmosis unit operates at approximately 80% efficiencyfor this particular waste water stream. The removal of between 10% and12.5% of the chlorides in the waste water stream by the filtration unit16 allows the reverse osmosis filter 114 to improve the efficiency to asmuch as about 90% to 95%.

The preferred embodiment is illustrated with a pretreatment step inwhich activated carbon, organo clay, acids, and oxidizing chemicals areused to pretreat the waste water stream. Alternatively, polymers aloneor in combination with the activated carbon, organo clay, acids, andoxidizing chemicals are added in the pretreatment step to raise the pHof the solution.

According to the provisions of the patent statutes, I have explained theprinciple, preferred construction and mode of operation of my inventionand have illustrated and described what I now consider to represent itsbest embodiments. However, it should be understood that, within thescope of the appended claims, the invention may be practiced otherwisethan as specifically illustrated and described.

I claim:
 1. A method for treating water comprising the steps of:providing a stream of brine water having in solution organic materials,heavy metals comprising metals selected from one or more of iron,aluminum, magnesium and zinc, and chlorides with a portion of theorganic materials forming an emulsion therein, mixing organo clay withparticles of activated carbon, an acid selected from the groupconsisting of organic acids and mineral acids, and a peroxide compoundto form a particle mixture of organo clay and activated carbon fortreating the stream of brine water, contacting the particle mixture oforgano clay and activated carbon with the stream of brine water toremove the organic materials and the heavy metals from the stream ofbrine water, directing the particle mixture of organo clay and activatedcarbon and the stream of brine water into a filter system having acatalyst to form a clean chloride solution, directing the clean chloridesolution into a distillation unit, and removing water from the cleanchloride solution within the distillation unit.
 2. A method as set forthin claim 1 which includes: directing the clean chloride solution into acontainer having a sacrificial anode, and combining ions from the cleanchloride solution to form a chloride-based compound.
 3. A method as setforth in claim 1 which includes: directing the clean chloride solutioninto a mixing tank, adding carbonate metal cation chemicals and achemical selected from the group consisting of hydroxides and oxides toform a second mixture, and filtering the mixture to produce a purifiedeffluent for discharge.
 4. A method as set forth in claim 1 whichincludes: directing the clean chloride solution into a mixing tankhaving a consumable anode and a cathode connected by a power supply, andapplying a voltage between the consumable anode and the cathode toremove chloride from the clean chloride solution to produce a purifiedeffluent for discharge.
 5. A method as set forth in claim 1 whichincludes: directing the clean chloride solution into a reverse-osmosisprocessing unit.
 6. A method as set forth in claim 1 which includes:injecting the clean chloride solution into a well.
 7. A method fortreating water comprising the steps of: providing a stream of brinewater having in solution organic materials, heavy metals comprisingmetals selected from one or more of iron, aluminum, magnesium and zinc,and chlorides with at least a portion of the organic materials formingan emulsion within the brine water, mixing organo clay with particles ofactivated carbon to form a particle mixture of organo clay and activatedcarbon for treating the stream of brine water, contacting the particlemixture of organo clay and activated carbon with the stream of brinewater to remove the organic materials and the heavy metals from thestream of brine water, filtering the particle mixture of organo clay andactivated carbon and stream of brine water to remove the particles ofactivated carbon to form a treated chloride solution, and adding anoxidizing chemical to the treated chloride solution to remove toxicorganic materials to form a clean chloride solution.
 8. A method as setforth in claim 7 wherein: the oxidizing chemical includes a peroxidecompound.
 9. A method as set forth in claim 7 which includes: adding anacid selected from the group consisting of organic acids and mineralacids to the particle mixture of organo clay and activated carbon.
 10. Amethod as set forth in claim 7 which includes: directing the cleanchloride solution into a processing unit to perform a finishing process.11. A method as set forth in claim 10 wherein: the finishing process isselected from the group consisting of chemical product production,electrochemical production, reverse osmosis, distillation, and deep wellinjection on the clean chloride solution within the processing unit.